A density functional theory study was performed to analyze the electron donor-acceptor properties of the cis and trans isomers of a novel azobenzene-containing tetraphenylporphyrin (TPPN2PhC14H29) with different substituents (Br or TMS). In general, the trans isomers are better electron acceptors than the correspondent cis homologues. Their UV-vis spectra were also obtained and a comparison with available experimental results is included. According to these results, the azo compounds reported here are promising materials for the elaboration of dye-sensitized solar cells because their HOMO-LUMO gaps are close to 2 eV. Moreover, the energy of the high intensity absorption bands also fulfills the requirements needed for the operation of a solar cell built with TiO2 and the I(-)/I3(-) pair.